| Reference | [1]. RSC Adv. 2020;10(40):24017-24026. doi: 10.1039/D0RA04110F. Epub 2020 Jun 23.<br />
Mild deprotection of the N-tert-butyloxycarbonyl (N-Boc) group using oxalyl chloride.<br />
George N(1), Ofori S(1), Parkin S(1), Awuah SG(1).<br />
Author information: (1)Department of Chemistry, University of Kentucky, Lexington, Kentucky 40506, USA.<br />
We report a mild method for the selective deprotection of the N-Boc group from a structurally diverse set of compounds, encompassing aliphatic, aromatic, and heterocyclic substrates by using oxalyl chloride in methanol. The reactions take place under room temperature conditions for 1-4 h with yields up to 90%. This mild procedure was applied to a hybrid, medicinally active compound FC1, which is a novel dual inhibitor of IDO1 and DNA Pol gamma. A broader mechanism involving the electrophilic character of oxalyl chloride is postulated for this deprotection strategy.<br />
DOI: 10.1039/D0RA04110F PMCID: PMC7810210 PMID: 33456769<br />
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[2]. Org Lett. 2015 Jun 5;17(11):2832-5. doi: 10.1021/acs.orglett.5b01252. Epub 2015 May 22.<br />
Oxalyl chloride as a practical carbon monoxide source for carbonylation reactions.<br />
Hansen SV(1), Ulven T(1).<br />
Author information: (1)Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Campusvej 55, 5230 Odense M, Denmark.<br />
A method for generation of high-quality carbon monoxide by decomposition of oxalyl chloride in an aqueous hydroxide solution is described. The usefulness of the method is demonstrated in the synthesis of heterocycles and for hydroxy-, alkoxy-, amino-, and reductive carbonylation reactions, in several cases under milder conditions than previously reported.<br />
DOI: 10.1021/acs.orglett.5b01252 PMID: 26000869<br />
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[3]. J Chem Phys. 2006 May 14;124(18):184313. doi: 10.1063/1.2196409.<br />
Observation of dihalide elimination upon electron attachment to oxalyl chloride and oxalyl bromide, 300-550 K.<br />
Van Doren JM(1), Hogan KB, Miller TM, Viggiano AA.<br />
Author information: (1)Department of Chemistry, College of the Holy Cross, Worcester, Massachusetts 01610-2395, USA. [email protected]<br />
Rate coefficients have been measured for electron attachment to oxalyl chloride [ClC(O)C(O)Cl] and oxalyl bromide [BrC(O)C(O)Br] in He gas at 133 Pa pressure over the temperature range of 300-550 K. With oxalyl chloride, the major ion product of attachment is Cl2(-) at all temperatures (66% at 300 K); its importance increases slightly as temperature increases. Two other product ions formed are Cl- (18% at 300 K) and the phosgene anion CCl2O- (16% at 300 K) and appear to arise from a common mechanism. With oxalyl bromide, the Br2(-) channel represents almost half of the ion product of attachment, independent of temperature. Br- accounts for the remainder. For oxalyl chloride, the attachment rate coefficient is small [(1.8 +/- 0.5) x 10(-8) cm3 s(-1) at 300 K], and increases with temperature. The attachment rate coefficient for oxalyl bromide [(1.3 +/- 0.4) x 10(-7) cm3 s(-1) at 300 K] is nearly collisional and increases only slightly with temperature. Stable parent anions C2Cl2O2(-) and C2Br2O2(-) and adduct anions Cl- (C2Cl2O2) and Br- (C2Br3O2) were observed but are not primary attachment products. G2 and G3 theories were applied to determine geometries of products and energetics of the electron attachment and ion-molecule reactions studied. Electron attachment to both oxalyl halide molecules leads to a shorter C-C bond and longer C-Cl bond in the anions formed. Trans and gauche conformers of the neutral and anionic oxalyl halide species have similar energies and are more stable than the cis conformer, which lies 100-200 meV higher in energy. For C2Cl2O2, C2Cl2O2(-), and C2Br2O2(-), the trans conformer is the most stable conformation. The calculations are ambiguous as to the oxalyl bromide geometry (trans or gauche), the result depending on the theoretical method and basis set. The cis conformers for C2Cl2O2 and C2Br2O2 are transition states. In contrast, the cis conformers of the anionic oxalyl halide molecules are stable, lying 131 meV above trans-C2Cl2O2(-) and 179 meV above trans-C2Br2O2(-). Chien et al. [J. Phys. Chem. A 103, 7918 (1999)] and Kim et al. [J. Chem. Phys. 122, 234313 (2005)] found that the potential energy surface for rotation about the C-C bond in C2Cl2O2 is "extremely flat." Our computational data indicate that the analogous torsional surfaces for C2Br2O2, C2Cl2O2(-), and C2Br2O2(-) are similarly flat. The electron affinity of oxalyl chloride, oxalyl bromide, and phosgene were calculated to be 1.91 eV (G3), and 2.00 eV (G2), and 1.17 eV (G3), respectively.<br />
DOI: 10.1063/1.2196409 PMID: 16709112<br />
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[4]. Dalton Trans. 2017 Dec 12;46(48):17074-17079. doi: 10.1039/c7dt04054g.<br />
Real-time detection of oxalyl chloride based on a long-lived iridium(iii) probe.<br />
Wu C(1), Li G(2), Han QB(3), Pei RJ(4), Liu JB(5), Ma DL(1), Leung CH(2).<br />
Author information: (1)Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong, China. [email protected]. (2)State Key Laboratory of Quality Research in Chinese Medicine, Institute of Chinese Medical Sciences, University of Macau, Macao, China. [email protected]. (3)School of Chinese Medicine, Hong Kong Baptist University, Kowloon Tong, Hong Kong, China. (4)CAS Key Laboratory for Nano-Bio Interface, Division of Nanobiomedicine, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou, 215123, China. (5)Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong, China. [email protected] and School of Metallurgical and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou, China. [email protected].<br />
A series of luminescent iridium(iii) complexes were designed and evaluated for their ability to detect oxalyl chloride ((COCl)2) at ambient temperature. In the presence of (COCl)2, a double amidation reaction takes place at the diamino functionality of complex 1, leading to the switching-on of a long-lived red luminescence with a 9-fold enhanced emission. Complex 1 exhibited high sensitivity and selectivity, with a detection limit for (COCl)2 at 32 nM. Additionally, complex 1 can be used to detect (COCl)2 using a simple smartphone, allowing for the portable and real-time monitoring of (COCl)2.<br />
DOI: 10.1039/c7dt04054g PMID: 29188252<br />
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[5]. Am Ind Hyg Assoc J. 1995 Jan;56(1):74-6. doi: 10.1080/15428119591017358.<br />
Acute inhalation toxicology of oxalyl chloride.<br />
Barbee SJ(1), Stone JJ, Hilaski RJ.<br />
Author information: (1)Department of Environmental Hygiene and Toxicology, Olin Corporation, New Haven, CT 06511.<br />
The acute inhalation LC50 of oxalyl chloride was determined in rats following a one-hour exposure. Four groups of 10 animals per group were exposed to a concentration range of 462-2233 ppm. One set of six animals was exposed to a concentration of oxalyl chloride of 1232 ppm for one hour to evaluate the histopathological change to the lungs. The LC50 is 1840 ppm with the 95% confidence interval between 1531 ppm and 2210 ppm. Microscopically, the lungs from the treated animals exhibited acute bronchiolitis, exudate within the alveoli, and congestion. Pulmonary edema appears to contribute significantly to mortality produced by oxalyl chloride. A comparison of the acute one-hour LC50 of oxalyl chloride to that of hydrogen chloride, phosgene, phosphorus oxychloride, boron trichloride, and chlorine indicates that it shares a comparable degree of acute toxicity to hydrogen chloride and is significantly less toxic via inhalation than the latter four chemicals.<br />
DOI: 10.1080/15428119591017358 PMID: 7872205 [Indexed for MEDLINE]
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